JPS63205330A - Rigid vinyl chloride resin composition and open-cellular foam prepared therefrom - Google Patents

Abstract

PURPOSE:To obtain the title composition which can give an open-cellular foam easily and inexpensively in a large quantity by extrusion, by mixing a vinyl chloride resin prepared by a specified polymerization process with a specified processing aid, a specified stabilizer, a surfactant and a specified blowing agent. CONSTITUTION:A rigid vinyl chloride resin composition essentially consisting of a vinyl chloride resin (preferably of an average degree of polymerization of 300-600) prepared by a suspension polymerization process and/or a bulk polymerization process, an ultrahigh MW acrylic resin processing aid (preferably of an MW >=1,000,000), a lead salt stabilizer (e.g., dibasic lead phosphite), a surfactant (e.g., a combination of an anionic surfactant with a nonionic surfac tant) and a heat-decomposable blowing agent. By extruding this composition, an open-cellular foam of a rigid vinyl chloride resin whose production has heretofore been thought impossible can be easily produced in good efficiency by extrusion. This open-cellular foam is composed of a rigid vinyl chloride resin essentially excellent in chemical resistance and weather resistance and material properties such tensile strength and hardness, so that it can be widely used for underdrain pipes, various air filters, etc.

Description

Detailed Description of the Invention (Industrial Field of Application) The present invention is applicable to LA drain vibes, aeration vibes, various aeration pipes, sandbar piles, various air filters, solid-gas separation materials, solid - A resin composition for providing a novel hard vinyl chloride resin open-cell body used in a wide range of applications such as liquid separation materials, gas injection materials into liquids, deodorizing agent base materials, aromatic carriers, etc. and an open cell obtained from the composition.

(Prior Art) Conventionally, flexible urethane foam made by reacting saturated polyester or polyether with isocyanate has been well-known as an open-celled synthetic resin foam, and in addition, polyvinyl alcohol and α-starch as a cell forming agent have been widely used. P powder is added, formalized, and the starch is washed out with water.
Is there a VA type sponge?

In addition, as a method for obtaining an open cell made of vinyl chloride resin, Japanese Patent Publication No. 53-21898 and U.S. Patent No. 4,2
The methods described in Japanese Patent Publication No. 26,943, Japanese Patent Publication No. 58-50662, Japanese Patent Publication No. 5B-25369 and Japanese Patent Publication No. 58-58370 are known.

The invention described in Japanese Patent Publication No. 53-21898 is that ``A mixture containing at least one of a vinyl chloride emulsion homopolymer and a vinyl chloride emulsion copolymer, a plasticizer, and a blowing agent is formed into a sheet shape, and heated. When producing the foam, a paraffinic wax having 20 to 80 carbon atoms and an ester wax having 20 to 80 carbon atoms consisting of 1 (1i) or polyhydric alcohol ester of a higher aliphatic-basic acid is added to the mixture; In addition, at least one type of wax that is substantially incompatible with the vinyl chloride polymer is added to obtain an open-celled body.

The invention described in U.S. Pat. A method for producing an open cell sheet made of vinyl chloride resin, which comprises a heating step, and the composition consists of the following components.

1) 100 phr vinyl chloride resin, 2) 30 to 1
50 phr plasticizer, 3) 1 to 8 phr synthetic hydrocarbon wax (polyethylene depolymerization, ethylene polymerization, coal gas F 1s
1,500 to 7.00, manufactured by a process selected from the group including cher-Tropsch synthesis.
0 molecular weight, a softening point of 90 to 135°C, and a particle size of 10 to 100 microns), 4) 1 to 5 phr alkali metal-Zn stabilizer, 5) 2 to 10 phr thermal decomposition type. Organic blowing agents containing at least 60% azodicarbonamide.

The vinyl chloride resin used in the latter invention is “
Although the term "emulsion polymer" is not specified, it is clearly defined in the text that "vinyl chloride resin produced by emulsion polymerization is used", and all of the examples are chlorinated by emulsion polymerization. Since a vinyl resin is used, it is clear that, like the former invention, this invention is a method for manufacturing open-cell bodies by a coating method using an emulsion polymer resin.

These inventions can be summarized as follows.

1) Uses vinyl chloride resin produced by emulsion polymerization method, 2) It is a soft sheet-like product with a large amount of plasticizer added, 3) Uses a pyrolyzable organic blowing agent, 4) Contains l) as an essential component. Adding waxes (in the case of Japanese Patent Publication No. 53-21898), 2) Adding waxes and an alkali metal-Zn stabilizer (in the case of U.S. Patent No. 4,226,943), 5) Adding other necessary ingredients to make a paste-like paint; 6) Applying the above-mentioned paint onto a substrate and turning it into a gel to process it into a sheet; 7) Heat the above-mentioned sheet in a foaming furnace to foam it continuously. Make it into a foam.

Also, Japanese Patent Publication No. 5B-50662, No. 58-253
The three inventions described in Publication No. 69 and Publication No. 58-58370 are by the same applicant as the present invention, and form the basis of the present invention.

The invention disclosed in Japanese Patent Publication No. 58-50662 is that ``In contrast to vinyl chloride resins normally used for plastisol,
Plasticizers, mixed or composite stabilizers that combine organic stabilizers containing metals from group 1 of the periodic table and organic stabilizers containing zinc and other metals, and blowing agents, usually for forming closed cells. A mixture prepared by adding a thermally decomposable organic blowing agent powder such as azodicarbonamide, which is used as an azodicarbonamide, and other compounding agents as necessary, is heated and kneaded, and then processed by a method such as a calendering method or an extrusion method. This is a method for manufacturing an open-cell body, which is characterized in that the sheet is rolled into a sheet shape by a method, and then the sheet is heated to the decomposition temperature of the blowing agent.

The invention disclosed in Japanese Patent Publication No. 5B-25369 is based on ``a general-purpose vinyl chloride resin produced by a suspension polymerization method as a main component, and an organic stabilizer containing a metal from group Ⅰ of the periodic table and an organic stabilizer containing a metal from group Ⅰ of the periodic table. A combination with an organic stabilizer containing a group III metal, or an organic stabilizer containing both a metal of group 1 and a metal of group II of the periodic table, an anionic surfactant, and a nonionic Addition of a surfactant consisting of a combination with a surfactant or an anionic surfactant and a low degree of polymerization polyolefin or waxes, a plasticizer and azodicarbonamide, which is usually used for the production of closed cell cells. A mixture prepared by adding a pyrolytic foaming agent such as pyrolytic foaming agent and other compounding agents such as fillers as necessary is heated and kneaded, and then rolled into a sheet by a method such as a calendering method or an extrusion method. After that, the sheet is heated and foamed by passing it through a foaming furnace."

The invention disclosed in Japanese Patent Publication No. 58370/1983 discloses that 4.4'-
A method for producing an open-cell body, which is characterized by: heating and kneading a mixture containing oxyhis (benzene 1 to rad) and an anionic surfactant, forming it into a sheet, and then heating and foaming the sheet. be.

The technical ideas common to these three inventions are summarized as follows.

1) As a processing method, a sheet-like material is first made by a calendering method (or an extrusion method), and then heated again in a foaming furnace to foam it.

2) As the vinyl chloride resin, a resin obtained by suspension polymerization is used (only Japanese Patent Publication No. 5B-50662 uses an emulsion-type legal resin).

3) A soft vinyl chloride resin product containing a plasticizer in an amount of 55 to 80 phr.

4) Metals from group 1 of the periodic table and group ■ of the periodic table as stabilizers
Mixtures or composite stabilizers containing group metals are used.

5) Use a surfactant (not used in Japanese Patent Publication No. 58-50662).

There are 5 items.

The products of these inventions are suitable for applications such as automobile interior materials and upholstery materials, and therefore, many of them are laminated with backing materials such as knitted fabrics, plain woven fabrics, and nonwoven fabrics. However, for such uses, the above-mentioned Japanese Patent Publication No. 53-21898 and U.S. Patent No. 4,22
Although various inventions including the invention in Specification No. 6,943 are extremely effective, they are completely ineffective in the production of hard vinyl chloride resin products, especially molded products such as pipe-shaped products and flat plate-shaped products, which is the above-mentioned field of application. This is an inapplicable invention.

On the other hand, PVA sponge is hard when dry and has excellent strength, but it becomes soft when exposed to water or moisture, and cannot be used in the above fields of use. Further, complicated reactions such as acetalization are required, and polyurethane foams yield only coarse open cells, making them unsuitable for the above-mentioned fields of use.

(Problems to be Solved by the Invention) When manufacturing open-cell products made of hard vinyl chloride resin, it is inappropriate to add a large amount of plasticizer, and even if it is added (the purpose of the addition is to (It is used as a processing aid to facilitate processing, and is not intended to soften the material.) The amount is extremely small at 10 to 15 phr. Therefore, the thermal and kneading behavior of the raw material composition during processing is completely different from that of soft vinyl chloride resin products.

In addition, products such as pipes, flat plate products, and rod-shaped products are molded by extrusion, but in this case, the formation of open cells in the molded product must be done at the time it passes through the die of the extruder. The conventional method of rolling the sheet into a sheet using a calendar or extrusion method and then reheating the sheet to foam it to obtain an open cell body cannot be applied.

Therefore, in the case of open-cell products made of hard vinyl chloride resin, the resin is gelled and melted by heating and kneading in the extruder, and at the same time the blowing agent is decomposed and gasified, and then passed through the die of the extruder. At the same time, a process of foaming the foam and converting the foam into open cells is required.

These process requirements can only be achieved by a completely new technical idea not found in the conventional inventions, and this is the object of the present invention.

(Means for Solving the Problems) The present inventor has achieved the above objects of the present invention by the following present invention.

That is, the present invention provides a hard vinyl chloride resin composition characterized by having the following components (a) to (e) as essential components, and a hard vinyl chloride resin obtained by molding the composition by extrusion molding. Made of open cell foam.

(a) Vinyl chloride resin produced by suspension polymerization method and/or bulk polymerization method, (b) M high molecular weight acrylic resin processing aid, (c) Lead salt stabilizer, (d) Surfactant, and (e ) Pyrolytic organic blowing agent.

(Preferred Embodiments) Next, the present invention will be described in more detail by citing preferred embodiments of the present invention.

The vinyl chloride resin used in the present invention is a vinyl chloride resin produced by the so-called suspension polymerization method and/or bulk polymerization method, and is conventionally used mainly in calender processing methods and extrusion processing methods. Vinyl chloride resins produced by emulsion polymerization used in coating methods, that is, paste resins, are not suitable for the purpose of the present invention.

In addition, the vinyl chloride resin used in the present invention includes vinyl chloride straight polymers (vinyl chloride homopolymers) produced by suspension polymerization and/or bulk polymerization, vinyl chloride-vinyl acetate copolymers, vinyl chloride - Polymers containing vinyl chloride as a main component, such as ethylene copolymer and ethylene-vinyl acetate-vinyl chloride terpolymer, are also used. Of course,
These vinyl chloride resins may be used alone or in a mixed resin system in which a plurality of them are combined, and are not particularly limited.

Selection of the degree of polymerization of the vinyl chloride resin is extremely important in the present invention. This is because the flow characteristics of the resin during extrusion change greatly depending on the degree of polymerization of the vinyl chloride resin, and in other words, this change in flow characteristics is caused by a change in the polymerization degree of the vinyl chloride resin.
Melt viscosity (80℃) and under constant load (70Kg)
This is because it means a change in the number of cells (X 10" voice) and is closely related to the formation of open cells during extrusion of vinyl chloride resin.

This melt viscosity is also affected by the type and amount of processing aids used in conjunction with the vinyl chloride resin, the type of stabilizer, and other formulation examples (e.g. surfactants, lubricants, fillers, etc.). The most dominant factor is the degree of polymerization of the vinyl chloride resin.

PVC resins are sold in a wide range of grades, from products with an average degree of polymerization of 300 to 600 to products with a high (ultra-high) degree of polymerization of 3,000 to 6,000.
For the composition and open cell of the present invention, those having an average degree of polymerization of 300 to 600 are preferred, and more preferably 400 to 500. If the polymerization degree is higher than this, for example, if the average polymerization degree is 700, which is generally commercially available, the resin flow (discharge condition and discharge amount) during extrusion molding will be poor, and the appearance of the product will be poor. And the open cell structure also deteriorates. This is thought to be due to an increase in melt viscosity due to an increase in the degree of polymerization of the resin, but if the heating temperature during molding and kneading is increased to lower the melt viscosity of the resin, an abnormal high temperature will occur in the extruder and the resin will deteriorate. This is not preferable because it will result in

The degree of polymerization of the vinyl chloride resin also changes depending on the stabilizer used therewith. In the invention of Japanese Patent Application No. 61-251325 previously filed by the present inventors, a -Zn-based liquid stabilizer was used as the stabilizer, but in this case, a resin with an average degree of polymerization of 700 is optimal; Low polymerization degree resins with an average polymerization degree of 400 to 500 cannot be used alone (causing cell roughening and the appearance of extruded products is extremely poor), and they cannot be used as processing aids for resins with an average polymerization degree of 700. It was only possible. In the case of the present invention, an inorganic lead salt-based stabilizer is used as the stabilizer, as described later, but even in this case, the present invention has an average polymerization degree of 700 as described above.
The one was inappropriate.

In the case of compositions and open cell bodies of the invention, processing aids (
(also called modifier) is an extremely important means, and its selection is also an extremely important factor in achieving the objective of the present invention.

In general, processing aids (or modifiers) for vinyl chloride resins include: 1) those based on butadiene resins such as ABS and MBS, 2) polyethylene, chlorinated polyethylene (cPE), and ethylene-vinyl acetate. 3) those based on olefin resins such as copolymers (EVA), 3) acrylic esters (
RA) or methacrylic acid ester (RMA) resins as a base; 4) condensation resins as a base; and 5) others.

1) Processing aids are mainly used to improve the impact resistance of hard vinyl chloride resin products, such as ABS, MB, etc.
Although S and the like are well-known, they are unsuitable as processing aids for the compositions and open-celled cells of the present invention. That is, when ABS or MBS is used in combination with the composition of the present invention and the open cell material, it is certainly effective in improving the impact properties of molded products;
The desired open-celled foam will not be obtained at all.

This is copolymerization (or graft polymerization) of ABS, MBS, etc.
This is thought to be due to the fact that the rubber component among the components exists heterogeneously in the molten composition of the vinyl chloride resin.

Among the processing aids mentioned in 2), CPE was particularly effective for the composition and open-celled foam of the present invention, and EVA showed some effects, but these effects were not affected by the processing aids mentioned in 3) below. This is a additive or complementary effect in combination with acrylic resin processing aids, especially ultra-high molecular weight acrylic resin processing aids, and excellent open-celled cells cannot be obtained with these EVA processing aids alone. .

Effective CPEs in the present invention include Eraslen 301A, 401A, and 351A1 manufactured by Showa Yuka ■ Osaka Soda ■
Daisolak G-235, H-135, etc. manufactured by E
As the VA, Soabrene CI manufactured by Nippon Gosei Kagaku ■ is effective.

The processing aids listed in 3) are collectively called acrylic resin processing aids, and are originally used to improve the processability of resins, improve the impact resistance of molded products, impart a matte effect, and improve the surface of molded products. It has been used for the purpose of improvement, etc. Examples of improving processability in extrusion molding (and blow molding) are: 1) improvement of surface gloss, 2) reduction of extruder torque, 3) prevention of retention deterioration. The following effects have been pointed out: 4) prevention of drawdown, 5) increase in hot melt strength, and 6) increase in discharge amount.

Examples of these acrylic resin-based processing aids include Metablane P-501 and P-551 manufactured by Mitsubishi Rayon ■, Kane Ace PA-11 and PA-20 manufactured by Kanebuchi Chemical ■, and Hyblen 401 manufactured by Nichibei Zeon ■. .402, BTA-101 manufactured by Kureha Kagaku ■, acryloid manufactured by Rohm & Haas, -120ON, -12OND1, -125, K-147, etc. However, these conventional acrylic resin-based processing aids are not effective alone as processing aids in the present invention, but like the CPE and EVA, they have a mutual effect in combination with ultra-high molecular weight acrylic resin-based processing aids. This is effective in terms of complementary or complementary effects.

The effective processing aid in the present invention is an ultra-high molecular weight acrylic resin processing aid, and examples of this product include Metablane P-530 and P-5 manufactured by Mitsubishi Rayon ■.
31 and Kaneace PA-50 manufactured by Kanebuchi Kagaku ■, but particularly effective are Metablane P-530 and P-531.
It is.

According to the company's catalog, this ultra-high molecular weight acrylic resin processing aid Metablane P-530 has an apparent specific gravity of 0. '35g/cc true specific gravity 1, '15g/cc particle size
30 mesh bath 98% or more volatile content 1.0
% Color: White in appearance, 1) Gelation promotion effect, 2) Effect on foam extrusion molding, 3) Effect on soft leather foaming, 4) Effect on soft calender molding, 5) Improvement in secondary formability. It is said to have the following characteristics: 6) improved moldability of high filler content molded products, 7) improved injection moldability, especially jetting, and 8) prevention of eye stain during extrusion molding. In particular, in 2) above, "Effects on foam extrusion molding," it is pointed out that it is possible to maintain high temperature and high foaming properties and form uniform cells for foam extrusion molding of hard vinyl chloride resin. There is.

These characteristics are fully exhibited in uninvented compositions and open-celled cells, and they show particularly excellent effects in combination with CPE, and can be said to be an indispensable processing aid in the practice of the present invention.

The distinction between ultra-high molecular weight acrylic resin processing aids and ordinary acrylic resin processing aids lies in their molecular weights.While the molecular weight of ordinary acrylic resin processing aids is 300,000 to 500,000, The molecular weight of the ultra-high molecular weight acrylic resin processing aid is approximately 1,000,000 or more, preferably 1,500,000 or more.

Therefore, when carrying out the present invention, processing aids should be selected using these molecular weight categories as a guide.

The amount of these processing aids added differs for each of CPE, ordinary acrylic resin processing aid, and ultra-high molecular weight acrylic resin processing aid. Although the former two are not effective on their own to obtain excellent open-celled cells, they provide a complementary or complementary effect in combination with ultra-high molecular weight acrylic resin processing aids. However, the roles of CPE and acrylic resin processing aids are different, and therefore the amounts added thereof are also different.

That is, CPE is effective in appropriately lowering the melt viscosity of the vinyl chloride resin and facilitating foaming due to decomposition of the blowing agent. Therefore, the amount added is 5 to 20ph
r (means parts by weight added to 100 parts by weight of vinyl chloride resin; the same applies hereinafter), which is relatively large. Furthermore, the same level of consideration may be given to the case where an EVA-based modifier is used instead of CPE.

On the other hand, general acrylic resin processing aids such as Metablen P-501 are effective in imparting smoothness and gloss to the surface of extruded products, and addition of about 1 to 3 phr is enough to achieve this effect. However, in the case of CPE, it is not necessary, and it is effective to use it in combination when using an EVA-based modifier.

On the other hand, ultra-high molecular weight acrylic resin processing aids have the effect of forming fine and homogeneous cells by decomposing the blowing agent and increasing the expansion ratio, and are used in a range of 2 to 15 phr.

The stabilizers used in the present invention are very specific and specific. In the above-mentioned conventional invention, alkali metal-Z
N-type stabilizers or stabilizers containing metals from Group 1 of the Periodic Table and Group Ⅰ of the Periodic Table were used, but in the present invention, these stabilizers have thermal properties, especially dynamic thermal properties. Very bad.

This has long been known as the biggest drawback of stabilizers containing alkali metals or Group 1 metals of the periodic table.
Japanese Patent Publication No. 53-21898 or U.S. Patent No. 4,2
As in the specification of No. 26,943, there are no problems in the case of paste compositions, but as in Japanese Patent Publications No. 58-50662, No. 58-25369, and No. 58-58370, processing involving heating and kneading However, its dynamic heat resistance has been a problem. The biggest problem with compounded compositions containing these stabilizers is thermal deterioration of the resin during kneading. This thermal deterioration is accompanied by discoloration of the resin and baking onto the roll surface. In extreme cases, the resin turns black and gives off a foul odor.
May be accompanied by corrosion of the roll surface. These changes are further increased when the above-mentioned stabilizers are used in the formulation of the hard vinyl chloride resin of the present invention. Therefore, in the invention of the above-mentioned Japanese Patent Application No. 61-251325, stabilizers containing metals of group 1 and group 2 of the periodic table are often used, and at the same time, these stabilizers are made into open cells. It was necessary to add an ultra-heat-resistant stabilizer such as tin mercaptide to the extent that the properties were not impaired. This tin-based stabilizer is very expensive and the amount added is relatively large at 2 to 3 phr, making the process complicated and economically disadvantageous.

As a result of intensive research in order to eliminate the drawbacks of these stabilizers, the inventors of the present invention discovered that so-called lead salt stabilizers are extremely suitable as stabilizers for the compositions and open-celled cells of the present invention. It was found that this shows that

The lead salt stabilizers mentioned above have been used for a long time for vinyl chloride resins, and are known to have excellent heat resistance and weather resistance. It is used as a stabilizer for vinyl resin vibes and vibe joints. It is surprising that this historical lead salt-based stabilizer is effective as a stabilizer for the compositions and open cell structures of the present invention, and that it can be used alone. The formulation and economic advantages of the invention are significant.

Generally, lead stabilizers are classified into lead salt stabilizers and lead soap stabilizers, as shown in Table 1 below. The stabilizer used in the present invention is a lead salt stabilizer that has almost no lubricity, and the lead soap stabilizer has too strong lubricity in the present invention and is not suitable for use alone. It is not possible to obtain open cells.

Among lead salt stabilizers, dibasic lead phosphite (commonly known as L-F
O3), tribasic lead sulfate (commonly known as TS) and lead white show excellent suitability. Table 2 below shows a comparison of the heat resistance of the alkali metal-7nj stabilizer and the alkali metal-Zn+SnJ stabilizer used in the conventional inventions and the above L-FO3.

These comparisons were made using [alkali metal-ZnJ stabilizer (manufactured by Atega Argus Co., Ltd., mark FL-30] in place of the stabilizer (L-FO3) used in the blended composition of Example 1 of the present invention described later). , liquid stabilizer) (comparative example 1), similarly the above mark-FL-30
An example using 2 phr and 2 phr of an alkali metal-Zn+SnJ-based stabilizer (Katsuyama Kogyome, TM-181FST, Sn mercaptite-based liquid stabilizer) (Comparative Example 2) and an example using Example 1 described below as is ( present invention)
This is a comparison of their heat resistance.

It can be seen from Table 2 that L-FO3 has thermal stability that is several orders of magnitude better than that of the comparative example.

These lead salt stabilizers may be used alone or in combination in the present invention. In particular, in the present invention, L-FO
A combination of 5 and TS gives excellent results.

~-1-1 lead salt 7,''''' 1 bear 38 quantity seven layers book. . 3. ．． 5shi) 2 White powder 86・826・
7 Dibasic lead phosphite white powder 83. 6.
92PbO・Pb11PO3・1/2H20 Itoshima Potato 6
Name: %lq Lead White powder 76.0ゝ 4.6 Silica gel co-precipitated silicon White powder 43-64%; 3.
．． 0~Acid lead PbSi03PbS1O3-,1 lead stone゛,, cps 1 7 6” 7 amount
Nanajushin Gor71 ¥3”! -White powder °5ゝ °4
"-2- Comparative Example 11!: Lump/L Negative Go, - Comparative Example 2 6
Stable at 0m1n Discoloration and odor generation at 25m1n Stable at 60m1n Stable at 60m1n The above heat resistance test was performed on a sample with a diameter of 9 inches and a length of 2
Each composition was kneaded at the above-mentioned temperatures using a 0-inch roll, wound around the roll (thickness: 0.4 mm), and samples were taken every 5 minutes to observe the condition. .

In the composition and open cell body of the present invention, a lead salt stabilizer is used for the hard vinyl chloride resin, which is completely unexpected from the conventional invention. As mentioned above, this lead salt stabilizer has an average degree of polymerization of 30.
It is suitable for vinyl chloride resins with an average polymerization degree of 0 to 600, preferably 400 to 500, but is unsuitable for vinyl chloride resins with an average degree of polymerization of 700 or more, and excellent open-celled cells cannot be obtained. Ta. The reason for this is not entirely clear at present, but it is presumed that the temperature-viscosity characteristics of the processed vinyl chloride resin film and the decomposition temperature of the blowing agent have some kind of influence.

The amount of lead salt stabilizer used in the present invention is 1.0 to 5.
in the range of 0 phr, more preferably 1.5 to 2.5 phr
is within the range of If the amount exceeds 5.0 pir, the decomposition of the blowing agent will be excessively accelerated, and gas will be released from the molded product when it comes out of the extruder, resulting in homogeneous and normal open cells. I can't get a body. If it is less than 1.0 phr, the heat resistance of the blended composition will be affected, and if it is less than 1.0 phr, the open-celled material of the present invention cannot be stably obtained.

On the other hand, small additions of lead soap stabilizers in the range of 0.1 to 0.5 phr are effective in improving the extrusion properties of the formulated compositions of the present invention; Rather than being limited, it should be viewed as ``utilizing the slipperiness'' of lead soap stabilizers. However, unlike nonionic surfactants and their substitutes, low-density polyolefins or waxes, the use of metal soap-based lubricants has a sharp effect on the blended composition, so the selection and amount used must be determined carefully. should be done carefully.

In the present invention, the use of a surfactant is an extremely important factor as well as the selection of a stabilizer, and the combination of an anionic surfactant and a nonionic surfactant is a desirable basic requirement. On the other hand, when an anionic surfactant is used alone, a molded product with excellent open cells cannot be obtained, and the same is true when a nonionic surfactant is used alone, so a combination of both is a preferable condition.

Types of anionic surfactants include higher fatty acid salts,
2nd edge higher fatty acid salt, higher alkyl dicarboxylate, 1st edge higher alcohol sulfate ester salt, S secondary higher alcohol sulfate ester salt, primary alkyl sulfonate, secondary alkyl sulfonate, higher alkyl disulfone Acid salts, sulfated fatty acids and fatty acid salts, sulfonated higher fatty acid salts, higher alkyl phosphate ester salts, sulfuric acid ester salts of higher fatty acid esters, sulfonate salts of higher fatty acid esters, condensates of higher fatty acids and proteolytic amino acids, higher Condensates of fatty acids and amino acids, alkylol sulfate salts of higher fatty acid amides, alkyl sulfonate salts of higher fatty acid amides, alkyl carboxylate salts of higher alkyl sulfonamides, sulfosuccinic acid ester salts, alkylbenzene sulfonates, Alkylphenol sulfonates, alkylnaphthalene sulfonates, formalin condensates of alkylnaphthalene sulfonic acids, sulfonates consisting of alkyldiphenyl and many other rings, ketone compounds of alkylaryl sulfonates, petroleum sulfonates, etc. used.

Nonionic surfactants include glycerin esters of fatty acids, glycol esters of fatty acids, pentaerythritol esters of fatty acids, sucrose esters of fatty acids, sorbitan and mannitan esters of fatty acids, higher alcohol condensates, higher fatty acid condensates, and higher alkyl amines. Condensates, higher fatty acid amide condensates, higher alkyl mercaptan condensates, alkylphenol condensates, polypropylene oxide condensates, and the like are used.

Examples of these surfactants that are actually commercially available include Liporan 1400 (α-olefin sulfonate) manufactured by Lion ■ for anionic surfactants, and Liporan 1400 (α-olefin sulfonate) manufactured by Lion ■ for nonionic surfactants. Knox NC-
2Y (polyoxyethylene alkyl allyl ether)
There is. All of these are extremely useful as surfactants for use in the compositions and rigid open cell foams of the present invention.

In the case of nonionic surfactants, these surfactants can be replaced with polyolefins such as liquid polypropylene and low polymerization degree polyethylene, or waxes. Surprisingly, the open-celled foam of the present invention obtained by these alternatives has no inferiority in comparison to the case where a nonionic surfactant is used, and there are no problems in the process. Needless to say, in this case as well, it is necessary to use an anionic surfactant in combination.

As liquid polypropylene, LPP- manufactured by Ube Industries ■
Examples of N108, low degree of polymerization polyethylene include Sunwax (decomposition product of high molecular weight polyethylene) manufactured by Sanyo Kasei ■, Neowax (polyethylene by-product) manufactured by Cheap Oil ■, and Mitsui High manufactured by Mitsui Petrochemical ■. There are waxes (low polymerization degree polyethylene), etc., and any type can be used. As waxes, Hoechst Wax OP manufactured by Hoechst Japan ■ and Nisseki Micro Wax 155 and 180 manufactured by Nippon Oil ■ can be used effectively.

The amount of these surfactants, polymerized polyolefins, or waxes used is generally in the range of 0.5 to 5.0 phr, more preferably in the range of 1.0 to 3.0 phr.

Addition of a blowing agent is also an important requirement in the present invention. As the blowing agent used in the present invention, a general pyrolyzable organic blowing agent is suitable. These blowing agents include azodicarbonamide (ADCA), dinitrosopentamethylenetetramine (DPT), valatoluenesulfonylhydrazide (TSH), 4,4'-oxybisbenzenesulfonylhydrazide (OBSH), azobisiso Butyronitrile (AIBN) etc. are used, especially A
DCA and 0BSH, alone or in combination, are extremely useful in the practice of this invention.

This pyrolytic organic foaming agent is a foaming agent that has traditionally been used to foam vinyl chloride resins, polyethylene, EVA, polystyrene, and various rubber products, but all of these foamed products are closed-cell foams. be. Furthermore, in the case of vinyl chloride resins, whether the resin is an emulsion polymer or a suspension polymer, usually only closed cell products can be obtained. 58
In the case of Publication No. 58370, an open-celled cell was obtained, but all of these were soft compound systems containing a large amount of plasticizer, and only sheets were obtained. It relies on a two-stage foaming method in which it is molded into a shape and then passed through a foaming furnace to foam, and as in the present invention, molded objects such as pipes and plate-shaped objects are produced using a hard compound system and an extrusion method using a one-stage method. Moreover, there have been no examples of its use in the past in which open-celled cells were obtained.

The amount of these pyrolyzable organic blowing agents added in the present invention is determined based on the type of blending system consisting of vinyl chloride resin, processing aid, stabilizer, and surfactant, the desired expansion ratio and desired air permeability of the molded part. It varies depending on the situation, but it is generally 0.5 to 10.
', 0 phr <7) with range test, preferably 1.0
The range is from 3.0 phr to 3.0 phr.

In the case of the compositions and rigid open cell bodies of the invention, the addition of powdered fillers such as calcium carbonate is also often effective. It acts as an auxiliary agent that supports the escape and/or diffusion of decomposed gas generated from the blowing agent, and compared to a blended system without the addition of powder fillers, the homogeneity of open cell pores and the stability of air permeability are improved. Are better.

In addition to the above-mentioned calcium carbonate, talc, silica, aluminum hydroxide, finely powdered wood flour, and the like can be used as the powder filler. The amount of these powder fillers added is generally in the range of 1.0 to 50.0 phr, more preferably in the range of 5.0 to 15.0 phr, and excessive addition may result in homogeneous foaming of the molded product. Care must be taken as this may impair open cell properties.

Furthermore, in the case of the composition and rigid open-celled foam of the present invention, the molding method is an extrusion method, so it is important to design the lubricity of the compounded composition. Nonionic surfactants or low-polymerization degree polyolefins or waxes as substitutes for them also have lubricity in themselves, but although their action as an external lubricant is effective, their action as an internal lubricant is not satisfactory. Can not do it. Therefore, in the case of the present invention, the addition of internal lubricants such as fatty acid esters of polyhydric alcohols is preferred, for example Roxiol G-12 and G-
16 mag is useful.

Further, in the present invention, a metal oxide such as zinc oxide may be optionally added to adjust the thermal decomposition temperature of the thermally decomposable organic blowing agent.

Furthermore, in the present invention, the addition of small amounts of plasticizers such as DOP, BBP, and TCP is often useful as a means of increasing internal slipperiness.

Further, in the present invention, coloring pigments such as titanium oxide, carbon black, chrome yellow, and watching red can be added arbitrarily and appropriately. However, when using iron compound pigments such as Bengara, the foaming and decomposition conditions of the compounding system will change, so it should be used after conducting experiments in advance and confirming whether there are any changes to the processing conditions.

The above-mentioned essential components and optional components constituting the vinyl chloride resin composition of the present invention include the desired shape (pipe, plate-like body, rod-like body, etc.), expansion ratio, air permeability, etc. of each molded product. After weighing or measuring a predetermined amount of each material depending on the properties required for the product, they are mixed and stirred using a high-speed stirrer, such as a Henschel mixer.

This mixing and stirring step is a very important step to obtain a homogeneous blended composition of the present invention. This is necessary in order to smoothly supply the composition from the hopper to the extruder when molding these blended compositions by extrusion, and to maintain stable discharge conditions from the extruder.
This is necessary to prevent variations in the foaming ratio and air permeability of the product.

Stirring with a Henschel mixer is preferably carried out at a temperature range of 80 to 110°C. In this temperature range, components such as surfactants, waxes and lubricants are dissolved, uniformly dispersed and absorbed into the vinyl chloride resin. Further, aggregated particles of the blowing agent are dispersed, and the dispersed fine particles of the blowing agent form a uniform mixed state with the resin component in the primary particle region. Further, in this temperature range, no partial gelation of the resin or thermal decomposition of the blowing agent occurs, so there is no problem in ensuring the above performance.

In practice, the powder composition heated to a temperature of 80 to 110° C. is mixed and stirred, then charged into a cooler mixer cooled with cooling water, and then supplied to an extruder for molding. Through this cooling step, the powder composition of the present invention becomes extremely smooth and has excellent fluidity. If a powder composition at a temperature of 80 to 110°C is fed directly to the extruder hopper without cooling, not only will the flow into the extruder become unstable, but heat accumulation in the composition will cause thermal deterioration of the resin. A reaction occurs, leading to an abnormal temperature rise, which results in blackening of the resin and thermal decomposition of the blowing agent, so care must be taken.

The extruder used for molding the above resin composition of the present invention is a non-vent type, and may be either a single screw type or a twin screw type. For example, when the average degree of polymerization of the vinyl chloride resin used in the composition is 450, the temperature conditions during molding are the temperatures at each position of the cylinder shown in FIG. =
120℃, C3=140℃, C4=150℃, C3=1
The standard conditions are 60° C., H (head part) = 170° C., and screw rotation speed 60 rpm (screw diameter 40 mm).

Discharge amount (for orifice thickness 2mm and width 39mm)
For the powder composition of the present invention which has not been previously subjected to the above processing using a Henschel mixer, the amount is approximately 3o0 g/min, but for the powder composition of the present invention that has been heated and stirred at 110°C for 5 minutes, immediately cooled and pre-processed. 450 g/min for composition
, the discharge amount increases by 1.5 times that in the above case, and moreover, a stable discharge amount can be obtained.

In the extrusion molded product of the present invention obtained in this way, the air bubbles are collapsed by friction on the contact surface with the die, forming a film on the surface, so when measuring the air permeability of the molded product, this film is Measure by grinding with an electric plane or grinder.

The air permeability is measured according to JISP-8117r paper and paperboard air permeability test method.

The principle of this test method is that the air volume of 100 mu is 645 mrn.
The time (seconds) it takes to pass through an object with an area of ' is measured, and this value represents the air permeability of the object.
Measure using. Expressing these values using specific product examples, for example, filter paper No. 2 takes 1.5 to 1.6 seconds, filter paper No. 003 takes 2.6 to 2.7 seconds, and filter paper No. 5C takes 10.6 to 10 seconds. .7 seconds, newspaper 22.5 to 24.
2 seconds, glass fiber filter Millipore AP2
0-055-00 or 0.7 to 0.8 seconds.

On the other hand, the hard open-celled foam according to the present invention can be obtained in a range of 1.0 to 5.0 seconds. This value is No, 2
This corresponds to the air permeability of filter paper No. 3. Of course,
This value can be changed depending on the distribution composition of the composition of the present invention. For example, when the open-cell foam of the present invention is used as a filter element, the value ranges from Millipore AP20 grade to No.

It is possible to produce moldings such as plates with any air permeability using a filter paper edge of 50.

(Example) Next, the present invention will be explained in more detail by giving examples and comparative examples.

Example 1 and Comparative Examples 1 to 4 Assuming the amount of vinyl chloride resin to be 2.5 kg, each compounding agent was weighed according to the formulation shown in Table 4 below, and 105 to 1
9I1. which had been heated to 10°C. The mixture was placed in a Henschel mixer and stirred for 5 minutes. The rotation speed was 1480 rpm. After 5 minutes, immediately run cooling water at 740 rpm.
The mixture was cooled for 10 minutes at low speed rotation to obtain a powder composition of the present invention having a composition temperature of about 40°C. This powder composition was a very smooth powder with an angle of repose of about 20°.

Using the above composition, a single type extruder with a screw diameter of 40 mm (manufactured by Tanabe Plastic Machinery ■, VS4) equipped with a 2I39 mm flat die on the head (H)
Extrusion molding was performed using a 0.0 extruder, a motor of 11 KW, and a heater of 8.2 W. The heating conditions were based on Table 3 below (see Figure 1).

A thin smooth film was formed on the surface of the obtained flat plate molded product, but this was removed with an electric plane to a thickness of 3.0 m.
Air permeability was measured as a disk with a diameter of 35 mm. The properties of the extrudates are shown in Table 4 below.

γ 3 − +00 120 140 150 160
170100 120 +40 150 1
60 170 screws per time (1m60 (1) C1 to C5 in the above table indicate the heating zones, and the area from immediately after the hopper to immediately before the head (H) is divided into approximately 5 equal parts, and each zone is heated to an arbitrary temperature. It is adjustable.

(2) The flat die is used by incorporating it into the head.

As is clear from Table 4 below, Example 1 of the present invention using Metablen P-530, which is an ultra-high molecular weight acrylic resin processing aid, showed extremely excellent results; Comparative Example 2 using a resin-based processing aid showed slightly better results, but the results in all other cases could not be put to practical use. The processing aid of Comparative Example 3 is said to have a relatively high molecular weight among general acrylic resin processing aids, but from the results in Table 4, it is clear that the composition of the present invention and open cell It was unsuitable as a processing aid for body use.

and 4 - Vinyl chloride resin"l 100 100100100
100 Erasren 3018”2 10 10 1
0 10 10 Asahi Kochoku Metablane P-530"3 5 - - - -Metablane P-501"3 - 5 - - --Kane Ace PA-20"4 - - 5 -- -Kane Ace PA-50"4-- ---5 -L-FO3"
5 2 2 2 2 2 Liporan 1400"6 22222 Liponox NC-2Y"6 1 1 1 1 10 Xyol G-16'7 2 2 2 2 2 Blowing agent A
W-9”8 1.5 1.51.51.51.5
Jucal NS#100"9' 20 20
20 20 201) Appearance OxB △ ○
×82) Cell shape O× △ △ ×3) Water permeability OOO△ 0 4) Air permeability (sec), 1.8 oo 5.2
＞]OOo.

5) Specific gravity 0.28 - 0.58 0.70
-6) Viscosity (×103 voids) 29.3 22.23Q, 623.613.1 Notes 1 Made by Chisso ■ (average degree of polymerization 450) 12 CPE made by Showa Denko ■ 73 Made by Mitsubishi Rayon ■, P- 501 is a conventional acrylic processing aid, while P-530 is an ultra-high molecular weight acrylic processing aid.

$4 Acrylic resin processing aid 95 manufactured by Kanebuchi Kagaku ■
Disalt normal lead phosphate 96 manufactured by Eishin Kasei ■. Riboran 1400 manufactured by Lion ■ is an anionic surfactant, while Ribonox NG-2Y is a nonionic surfactant.

97 Internal lubricant manufactured by Henkel Hakusui ■ 78 ADCA foaming agent manufactured by Hydraulic Chemical ■ 99 Heavy calcium carbonate manufactured by Nitto Funka ■ 10 Characteristic evaluation is as follows.

l) Appearance: Judgment by visual inspection of the extruded product O: Good, △: Slightly good, ×S: Shark-skin-like ×B Two parts have swelling.

2) Cell shape: Judgment by visualizing the cross section of the extruded product 0: Good, Δ: Slightly bad, ×: Bad 3) Water permeability: Water colored with red ink was dropped on the cross section of the extruded product, and the permeation state was determined. Judgment: O: Fast, △: Slightly slow, ×: No penetration 4) Air permeability: ■Measurement load 557g with Toyo Seiki's new B type Gurley densometer No. 158, permeable area &45mrn'5) Specific gravity ; Calculated by calculation 6) Viscosity: Measured by Shimadzu flow tester CFT-500 Load: 70 kg, measurement temperature: 180°C Examples 2 to 7
and Comparative Examples 5 to 14 A composition of the present invention was prepared in the same manner as in Example 1 using the formulations shown in Table 5 below, and extrusion molding was performed in the same manner using this composition to obtain an open cell body of the present invention. Ta.

Incidentally, the criteria for characteristic evaluation are the same as those in Table 4 above.

(Left below) 1. Tribasic lead sulfate ---22- pb-stearate --- Mark 0F-15"4-- - - -
-Kuichiichiken Roxiol G-16222222 3≧Ln e (J1j8W to 9 3
3 3 3 3
3 charge road measurement NS#100 20 20 20
20 20 20 Sacrifice-Ichiri 1) Appearance ○ ○ ○ ○ 0
2) Cell shape ○ ○ ○ ○ ○
03) Water permeability ○ ○ ○ O○
04) Air permeability (sec) 2.4 3.5 3.6
2.8 3.1 4.85) Specific gravity 0.2
8 0.33 0.34 0.30 0.33 0.4
16) Viscosity (xlo3cps) 40.2 38.1
39.8 4B, 5 35.2 43.3 Note 11: EVA processing aid manufactured by Nippon Gohsei ■ (foaming formulation 12:
Ezdel wax 73 manufactured by Hoechst Japan ■ Low polymerization degree polyethylene “4” manufactured by Tetsu Seikagaku ■; Adeka Argus ■
Ba-Zn stabilizer (powder) 3--1-----2 0o OO△ △ △ OO0ooo
o △ △ △ ○ ○
○X × × × △ △
△ △ △ ×---->100
>100 >100 >100 >100
-0.21 0.25 0,26 0.29 0.
72 0.73 0.68 0.38 0.44 0.
3345.3 41,3 46.6 42.9 21
．． 4 28.8 35.7 4], 7 39.3 42
．． 6) Referring to Table 5 above, there is a difference between CPE and EVA-based processing aids in Examples 2 and 4. (The number of seconds is dog) Other than that, they are almost the same. This is almost the same even when the wax OP is replaced with low degree of polymerization polyethylene in the comparison between Examples 2 and 3.

Examples 5 and 6 are examples in which the stabilizer was replaced with tribasic lead sulfate (TS) from L-FO3, but there is almost no difference compared to Example 2, and the performance is equivalent to that of L-FO3. I understand.

Example 7 is an example in which CPE or EVA was not used as a processing aid, but compared to Examples 1 and 2, the air permeability was slightly lower and the specific gravity and viscosity were higher, but the appearance and cell shape were good. These processing aids are complementary processing aids to the ultra-high molecular weight acrylic resin processing aid, and the excellent open-celled foam of the present invention can be obtained without any practical problems even without the addition of these processing aids. I understand.

Comparative Example 5 uses a regular foaming stabilizer (
This is an example using a Ba-Zn-based composite stabilizer), and although the foaming itself shows excellent foaming, it does not result in open cells.

Comparative Examples 6 to 8 are examples in which either an anionic surfactant, wax, or low degree of polymerization polyolefin is not added, and the foaming itself shows excellent foaming, but does not become an open cell foam. From these results, it will be understood that in the case of the present invention, the combination of both is a very preferable requirement.

Comparative Examples 9 to 11 are examples in which a so-called lead salt stabilizer, lead stearate (PB-stearate), was used instead of a lead salt stabilizer, but the results are completely different from the case of a lead salt stabilizer. It exhibited poor properties such as appearance, cell shape, and air permeability, and was unsuitable as a stabilizer in the present invention.

Comparative Examples 12 and 13 are examples of the combined use of a lead salt stabilizer and pb-stearate, and although the appearance and cell shape of the molded products are good, the water permeability and air permeability are poor, making them unusable for practical use. It was something that didn't exist.

Comparative Example 14 is a combination of a Ba-Zn composite stabilizer and pb-stearate, and although the appearance and cell shape are good, the water permeability and air permeability are poor, and it cannot be put to practical use at all. Ta.

(Effects of the Invention) From the above results (Examples 1 to 7, Comparative Examples 1 to 14), it is clear that according to the present invention, open-cell bodies made of hard vinyl chloride resin can be easily produced by extrusion, which was previously considered impossible. It will be understood that it can be obtained efficiently.

In addition, when these open-cell bodies are obtained by extrusion, a resin having an average degree of polymerization of 300 to 600, more preferably 400
Vinyl chloride resin produced by suspension polymerization and/or bulk polymerization in the range of 500 to 500, single or in combination of ultra-high molecular weight acrylic resin processing aid, anionic surfactant and nonionic surfactant or a combination of an anionic surfactant and a wax or a low degree of polymerization polyolefin, and a pyrolyzable organic blowing agent such as ADCA,
If necessary, it is preferable to use blending examples of internal lubricants, fillers, pigments, etc., and the combination of these can create an excellent open-cell structure made of hard vinyl chloride resin, 5111-Noh-A.
-A, 1. ! It is surprising that this can be obtained. The compounding agents mentioned in "2.
Although it is not a new material, by combining the above-mentioned series of components, an excellent open-celled cell can be obtained easily, in large quantities, and at low cost.

The open-celled cell according to the present invention is made of a hard vinyl chloride resin that is wood-like and has excellent chemical resistance and weather resistance, as well as excellent material properties such as tensile strength and hardness. Up until now, only expensive ceramic sintered bodies and plastic sintered bodies have been used for applications such as slope water removal piles and pipes, aeration pipes for gray water and sewage, chemical filter media, and corrosive gas filter media. Since it can be suitably used for purposes that were previously unavailable, it can provide an extremely meaningful material for civil engineering work and other industries.

[Brief explanation of the drawing]

FIG. 1 is a diagram showing an example of temperature distribution in an extrusion molding machine used in the present invention. 1: Hopper, 2: Screw Applicant Kuchi N Seal Kogyo Co., Ltd. Figure 1 C5C4C3C2C1

Claims (18)

[Claims] (1) A hard vinyl chloride resin composition comprising the following components (a) to (e) as essential components. (a) Vinyl chloride resin produced by suspension polymerization method and/or bulk polymerization method, (b) Ultra-high molecular weight acrylic resin processing aid, (c) Lead salt stabilizer, (d) Surfactant, and (e) ) Pyrolytic organic blowing agent. (2) Average degree of polymerization of vinyl chloride resin is 300 to 60
The hard vinyl chloride resin composition according to claim (1), wherein the hard vinyl chloride resin composition has a hardness of 0. (3) The molecular weight of the ultra-high molecular weight acrylic resin processing aid is 1
1,000,000 or more, the hard vinyl chloride resin composition according to claim (1). (4) The hard material according to claim (1), wherein the lead salt stabilizer is one or more selected from the group consisting of dibasic lead phosphite, tribasic lead sulfate, and lead white. Vinyl chloride resin composition. (5) Claim (1) in which the surfactant is a combination of an anionic surfactant and a nonionic surfactant, or a combination of an anionic surfactant and a low polymerization degree polyolefin or waxes. The hard vinyl chloride resin composition described. (6) The hard vinyl chloride resin composition according to claim (1), wherein the pyrolyzable organic blowing agent is azodicarbonamide. (7) The hard vinyl chloride resin composition according to claim (1), in which an ultra-high molecular weight acrylic resin processing aid is used in combination with chlorinated polyethylene. (8) Claim No. 1 further containing a powder filler
) The hard vinyl chloride resin composition described in item 1. (9) The hard vinyl chloride resin composition according to claim (1), further containing additives such as pigments and lubricants. (10) An open-cell hard vinyl chloride resin foam formed by extrusion molding using a composition containing the following components (a) to (e) as essential components. (a) Vinyl chloride resin produced by suspension polymerization method and/or bulk polymerization method, (b) Ultra-high molecular weight acrylic resin processing aid, (c) Lead salt stabilizer, (d) Surfactant, and (e) ) Pyrolytic organic blowing agent. (11) Average degree of polymerization of vinyl chloride resin is 300 to 6
00 range, the hard vinyl chloride resin open cell body according to claim (10). (12) The open-celled hard vinyl chloride resin according to claim (10), wherein the ultra-high molecular weight acrylic resin processing aid has a molecular weight of 1 million or more. (13) Hard chloride according to claim (10), wherein the lead salt stabilizer is one or more selected from the group consisting of dibasic lead phosphite, tribasic lead sulfate, and lead. Open-cell vinyl resin material. (14) Claim (10) wherein the surfactant is a combination of an anionic surfactant and a nonionic surfactant, or a combination of an anionic surfactant and a low polymerization degree polyolefin or waxes. Open-celled hard vinyl chloride resin as described. (15) The open-cell hard vinyl chloride resin foam according to claim (10), wherein the pyrolyzable organic blowing agent is azodicarbonamide. (16) The open-cell hard vinyl chloride resin foam according to claim (10), in which an ultra-high molecular weight acrylic resin processing aid is used in combination with chlorinated polyethylene. (17) Claim No. 3 further containing a powder filler (
The open-celled hard vinyl chloride resin according to item 10). (18) The open-cell hard vinyl chloride resin foam according to claim (10), further containing additives such as pigments and lubricants.